Lubricants comprising novel cyclopentanes, cyclopentadienes, cyclopentenes, and mixtures thereof and methods of manufacture

ABSTRACT

Hydrocarbyl substituted cyclopentadienes, cyclopentenes, and cyclopentanes are synthetic lubricating compositions. The preferred structures contain 1 to 6 alkyl groups which have 4 to 36 carbon atoms and may have different and varying carbon chain structures. The cyclopentenes and cyclopentanes are prepared by hydrogenation from the corresponding cyclopentadiene intermediates. The cyclopentadienes are prepared by reaction with hydrocarylating agents or alcohols. Mixtures are also disclosed.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. application Ser. No. 909,305,filed Sept. 19, 1986, now U.S. Pat. No. 4,721,823, and acontinuation-in-part of Ser. No. 170,652 filed Mar. 15, 1988, nowabandoned.

FIELD OF THE INVENTION

This invention relates to novel hydrocarbyl-substitutedcyclopentadienes, hydrocarbyl-substituted cyclopentadienes,hydrocarbyl-substituted cyclopentenes, and mixtures thereof, and theiruse as lubricating compositions, and more particularly, this inventionrelates to novel hydrocarbyl cyclopentanes, hydrocarbylcyclopentadienes, hydrocarbyl cyclopentenes, and mixtures thereof, novelmethods for formation of the cyclopentadienes and their conversion tothe cyclopentenes and cyclopentanes, and use of the cyclopentanes,cyclopentadienes, cyclopentenes and mixtures thereof as lubricatingcompositions.

BACKGROUND

Cyclopentadiene, cyclopentene and cyclopentane and alkylated derivativesthereof are known in the art. Further, methods are known for preparationof alkylated cyclopentadienes and conversion of these materials tocyclopentenes and cyclopentanes. There is substantial interest incyclopentadienes, cyclopentenes, and cyclopentanes since cyclopentadieneis characterized by the unique property of being the most acidicaliphatic hydrocarbon known, having a pKa of 18, and also because itsreactions as a Diels-Alder diene are extremely facile. Because of thearomaticity of the cyclopentadiene anion (c--C₅ H₅ ⁻), cyclopentadieneis easily the most acidic of the simple hydrocarbons and in fact iscomparable in acidity to alcohols. This means that substantial amountsof the anion can be generated with alkoxides and even concentratedsolutions of hydroxide. Since it is uniquely stable, it can participatein the carbanion reactions of alkylation, acylation, carboxylation andthe like.

U.S. Pat. No. 3,255,267 to Fritz et al discloses the alkylation ofcyclopentadiene and monoalkylcyclopentadiene with a single primary orsecondary alcohol in the presence of a highly alkaline catalyst,including the disclosure of trialkylated and tetralkylated products.Fritz et al do not appear to contemplate using mixed alcohols foralkylation and the alkylcyclopentadiene products disclosed cannot havemore than two different alkyl groups, a single substituent derived fromstarting cyclopentadiene and the rest derived from the alcohol.

The cyclopentadienes described by Fritz et al contain primaryhydrocarbon substituents of up to 11 carbon atoms and secondaryhydrocarbons of structure R_(c) R_(d) CH, where R_(c) is selected from"hydrocarbon radicals free of aliphatic unsaturation, including alkyland aryl radicals, said radicals having from 1 to 10 carbon atoms;" andR_(d) is "a hydrocarbon radical free of aliphatic unsaturation,including alkyl and aryl radicals, said radicals having from 1 to 10carbon atoms,". An additional class includes R_(c) R_(d) =--CH₂(CH₂)_(n) CH₂ -- where n is an integer having a value of 1 to 10. Thus,Fritz et al teach compositions in which no more than two different kindsof hydrocarbyl groups may be present, and in which no more than onehydrocarbyl group may occur more than once. Thus, the products which canbe produced by Fritz et al are controlled by this disclosed alkylationreaction which uses only a single alcohol. In addition, Fritz et alteach that "Ethanol is by far the preferred primary alcohol since theyields obtained with this alcohol are much in excess of the yieldsobtained when employing other primary alcohols." Fritz et al present twoexamples of alkylation with primary alcohols with the following yieldsbased on cyclopentadiene:

Example 24: Ethanol plus cyclopentadiene--17.8% yield

Example 26: 2-Ethylbutanol plus cyclopentadiene--1.6% yield.

Applicants have discovered that the process improvement of removingwater from the reaction as it is formed greatly increases the yieldsobtained with primary alcohols to near quantitative levels and thatusing mixtures of alcohols provides an alkylation reaction whichproduces a wide variety of novel and useful alkylated cyclopentadienes.

U.S. Pat. No. 3,560,583 discloses cyclopentadiene compounds containingup to five substituents, which substituents can be independentlyhydrogen, alkyl, aryl or aralkyl. These compounds are prepared byreaction of a cyclopentadiene compound with benzyl halide or allylhalide, an alkali metal hydroxide and a quaternary ammonium saltcatalyst.

Polish patent No. 55,535 to Makosza, 1968, discloses indene compoundswhich contain alkyl substituents on the cyclopentadiene portion of themolecule. However, the working examples indicate that only a singlealkyl group or two allyl groups are present. U.S. Pat. No. 3,931,334discloses lubricant compositions which comprise substituted indans, theindan molecule being substituted by methyl and styryl.

In a thesis by Stephen S. Hirsch, University of Maryland, 1963, there isdisclosure of base catalyzed alkylation of cyclopentadienes utilizingalcohols to effect the alkylation. Included in this disclosure arealkylation reactions with benzyl alcohol to produce cyclopentadieneswhich can contain as many as five benzyl substituents. Also disclosedare 1,3-dialkyl indenes.

Polish patent No. 55,571 to Makosza discloses cyclopentadienes andprocesses for preparation of monosubstituted cyclopentadienes by the useof phase-transfer alkylation. The patent is limited to monosubstitutedcompounds with short chain alkyl groups.

The prior art contains numerous disclosures of methods for thepreparation of substituted cyclopentadienes but wherein the substituentsusually are short chain alkyl groups. The methods of preparation of suchmaterials vary but do include such processes as the reaction of thecyclopentadiene with alkyl halides in the presence of a base as in U.S.Pat. No. 2,953,607. Similar disclosures may be found in U.S. Pat. Nos.3,131,227, 4,547,603, 4,567,308, 3,560,583, 4,412,088, and 3,755,492. Ofparticular interest is 3,131,227 which discloses polysubstitutedcyclopentadienes such as pentamethyl and hexamethyl cyclopentadienewhich is prepared by a cyclization reaction. Also in U.S. Pat. No.4,567,308, alkyl cyclopentadienes and alkylated derivatives thereof areprepared by the vapor phase reaction of a cyclopentadiene derivative andan aliphatic lower alcohol in the presence of a basic catalyst. Thesecyclopentadienes and alkylated products are disclosed as being additivesfor synthetic rubbers, starting materials for resins and/or industrialchemicals.

In a publication by J. Denis, Journal of Synthetic Lubrication, Vol. 1,p. 201-219 (1985), there is disclosure of hydrocarbons which may be usedin lubricant compositions. Specifically mentioned in this publicationare cycloalkanes and in particular monoalkyl substituted cyclopentanes.This publication in a comparison of various hydrocarbon structuresincluding normal alkanes, alkanes branched by one or more alkyl chainsor by a ring, cycloalkanes and aromatics as base stocks for lubricants.

In a publication by Rong et al, Acta Chemica Sinica, Vol. 41, No. 10,Oct., 1983, there is disclosure of the use of polyethylene glycol as aphase transfer agent for halide alkylation of cyclopentadiene with alkylhalides. The products produced are monoalkyl substitutedcyclopentadienes. In a related article by Rong et al, Journal of ChineseUniversities, Vol. 4, page 576-580 (1983), there is disclosure of thesynthesis of alkyl substituted derivatives of cyclopentadiene by thephase transfer catalytic reaction of cyclopentadiene with alkyl halidesin the presence of potassium hydroxide and polyoxyethylene surfactantsas a catalyst. Only monoalkyl substituted cyclopentadienes are prepared.

U.S. Pat. Nos. 3,004,384, 3,356,704, 3,358,008, 3,388,180, 3,391,209,3,414,626, and 3,419,622 disclose polysubstituted cyclopentadienes andcyclopentanes but wherein the substituent is a short chain alkyl groupor allyl group. Finally, U.S. Pat. Nos. 3,751,500 and 3,636,176 discloseindene compounds which can contain short chain alkyl substituents whichare useful as perfume compositions.

In none of the prior art of which Applicants are aware are theredisclosures of poly-hydrocarbyl cyclopentanes, cyclopentadienes,cyclopentenes, and mixtures thereof which are useful as lubricantcompositions, which useful products may be prepared from novelhydrocarbyl-substituted cyclopentadienes. The present invention providessuch novel products as well as methods for their preparation and methodsfor their use.

SUMMARY OF THE INVENTION

It is accordingly one object of the present invention to providehydrocarbon-substituted cyclopentanes which are useful as lubricatingcompositions.

A further object of the invention is to provide novel and usefulcyclopentanes which are poly-hydrocarbyl substituted and which areprepared from the corresponding hydrocarbyl substitutedcyclopentadienes.

A still further object of the present invention is to providelubricating compositions which contain hydrocarbyl-cyclopentanes as alubricating component.

There are also provided novel intermediate compositions of matter whichcomprise hydrocarbyl-substituted cyclopentadienes andhydrocarbyl-substituted cyclopentenes, the cyclopentadienes andcyclopentenes also being useful as lubricating compositions.

Also provided by the present invention are lubricating compositionswhich comprise novel poly-hydrocarbyl substituted cyclopentadienes andpoly-hydrocarbyl substituted cyclopentenes.

Also provided by the present invention are lubricating compositionscomprising mixtures of hydrocarbyl cyclopentanes, hydrocarbylcyclopentenes, and/or hydrocarbyl substituted cyclopentadienes,optionally in admixture with a natural lubricant such as mineral oil orother synthetic lubricants as base fluids.

Further provided by the present invention are novel methods forpreparation of the hydrocarbon-substituted cyclopentadienes comprising aphase transfer method and an alcohol method.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In satisfaction of the foregoing objects and advantages of the presentinvention, there is provided as a broad embodiment of the invention, aclass of lubricating compositions which comprise one or morehydrocarbyl-substituted cyclopentanes. These hydrocarbyl-substitutedcyclopentanes include the individual compounds and mixtures of thehydrocarbyl-substituted cyclopentane compounds. The compounds are of thefollowing general formula: ##STR1## wherein in the above formula, eachR₁ is individually and independently selected from alkyl groups of 1 to4 carbons, each R₂ is individually and independently selected fromhydrocarbyl groups containing about 4 to 36 carbon atoms, preferably 8to 36 carbon atoms, more preferably 12 to 24 carbon atoms, z is 0, 1, 2or 3, and x is an integer ranging from 1 to 6, preferably 2 to 6, morepreferably 3 to 6, and x+z cannot be greater than 6. Preferred compoundswithin this group are those wherein each R₂ is individually andindependently selected from alkyl groups having about 8 to 24 carbonatoms, x is an integer of about 2 to 6, and more preferably is aninteger ranging from 3 to 6, and the total number of carbon atoms in theR₂ groups should preferably not exceed about 80.

In a further embodiment of the invention, there are provided novelcyclopentane compositions which are useful as lubricating compositionsand which are of the following general formula: ##STR2## wherein each R₁is individually and independently selected from alkyl groups of 1 to 4carbons, each R₂ is individually and independently selected fromhydrocarbyl groups having about 4 to 36 carbon atoms, preferablystraight or branch chained alkyl groups, z is 0, 1, 2 or 3 and y is aninteger ranging from 2 to 6, preferably 3 to 6, provided that when atleast 2 of the R₂ substituents contain alkyl groups of from 4 to 10carbon atoms, then y must be an integer of at least 3, y+z cannot begreater than 6. The total number of carbon atoms in the R₂ groups shouldpreferably not exceed about 80.

There are further provided by the present invention novelcyclopentadiene intermediate compounds which can be hydrogenated to thecyclopentanes referred to above, which intermediate cyclopentadienes areof the following general formula: ##STR3## wherein in the above formula,each R₁ is individually and independently selected from alkyl groups of1 to 4 carbon atoms, each R₂ is individually and independently selectedfrom hydrocarbyl groups, preferably straight or branch chained alkyl oralkenyl groups of 4 to 36 carbon atoms, preferably 8 to 36 carbon atoms,more preferably 12 to 24 carbon atoms, z is 0, 1, 2 or 3, and y is aninteger of from 2 to 6, preferably 3 or 4 to 6, and y+z cannot begreater than 6, provided that when up to four of the R₂ groups containfrom 4 to 11 carbon atoms, then y must be an integer of at least 5. Thetotal number of carbon atoms in the R₂ groups should preferably notexceed about 80.

The cyclopentadiene compounds of the above formula, referred to as novelintermediate compounds, are also included in a group of novellubricating compositions. Thus, polyhydrocarbyl substitutedcyclopentadienes of the following formula are useful as lubricatingcompositions: ##STR4## wherein in the above formula, each R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, each R₂ is individually and independently selected fromhydrocarbyl groups containing about 4 to 36 carbon atoms, preferably 8to 36 carbon atoms, more preferably 12 to 24 carbon atoms, z is 0, 1, 2or 3, and x is an integer ranging from about 1 to 6, preferably 2 to 6,more preferably 3 or 4 to 6, and x+z cannot be greater than 6. Preferredcompounds within this group are those wherein each R₂ is individuallyand independently selected from alkyl or alkenyl groups having about 8to 24 carbon atoms and x is an integer of about 2 to 5, and the totalnumber of carbon atoms in the R₂ groups should preferably not exceedabout 80. The cyclopentadienes of this formula may also be used asintermediates for hydrogenation to the cyclopentene and cyclopentanelubricants of the invention.

There are also provided by the present invention lubricatingcompositions which are partially synthetic lubricants and partiallynatural lubricants. These lubricating compositions comprise thehydrocarbyl substituted cyclopentanes, or the hydrocarbyl substitutedcyclopentandienes, or the hydrocarbyl substituted cyclopentenes, or anymixture thereof, in any proportions with a natural lubricant base suchas mineral oil. Also provided are mixtures of the synthetic lubricatingcompositions of the present invention with other synthetic lubricants sothat the resulting lubricating composition is a mixture of syntheticlubricants. Also included within the scope of the invention are mixturesof any or all of the synthetic lubricants of the present invention,alone or in admixture with other synthetic lubricants, or with naturallubricants.

Also provided by the present invention are methods for production of thehydrocarbyl-substituted cyclopentadiene compounds, one method comprisingthe single step reaction of cyclopentadiene or substitutedcyclopentadiene with a molar excess of a hydrocarbylating agent ormixture of such agents of the formula R₂ Y, wherein R₂ is as describedabove and Y is a leaving group, preferably a halogen, in a reactionvessel containing an aqueous alkaline solution and a phase transfercatalytic agent. In a second method for preparation of the novelcyclopentadienes, cyclopentadiene or substituted cyclopentadiene isreacted with a molar excess of a primary or secondary alcohol or mixtureof such alcohols of the formula R₂ OH wherein R₂ is as described abovein the presence of a basic catalyst at elevated temperatures, and withremoval of water as it is formed, and recovering the product.

BRIEF DESCRIPTION OF THE DRAWINGS

Reference is now made to the drawings accompanying the applicationwherein:

FIG. 1 is the ¹³ C nmr spectrum of alkylcyclopentadiene;

FIG. 2 is the ¹³ C nmr spectrum of alkylcyclopentene; and

FIG. 3 is the ¹³ C nmr spectrum of alkylcyclopentane.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention is broadly concerned with lubricating compositionswhich comprise certain hydrocarbyl cyclopentanes, hydrocarbylcyclopentadienes, hydrocarbyl cyclopentenes, or mixtures thereof, andmethods of preparation. The invention is also concerned with a class ofnovel cyclopentanes and corresponding cyclopentadiene and cyclopenteneintermediates, methods for their preparation and methods for conversionof the cyclopentadienes to the cyclopentane lubricants.

In a main embodiment of the invention, novel synthetic fluids which arelubricating compositions comprise a group of polyhydrocarbyl-substitutedcyclopentanes of the following formula: ##STR5## wherein in the aboveformula, each R₁ is individually and independently selected from alkylgroups of 1 to 4 carbon atoms, each R₂ is individually and independentlyselected from hydrocarbyl groups containing from about 4 to about 36carbon atoms, preferably 8 to 36 carbon atoms, more preferably 12 to 24carbon atoms; and preferably is a straight or branch chained alkyl groupof 4 to 36 carbon atoms, preferably 8 to 36 carbon atoms; z is 0, 1, 2or 3, and x is an integer ranging from 2 to 6, preferably 3 to 6, andx+z cannot be greater than 6.

It will be understood that in Formula I as well as in Formulae II toVIII described hereinafter, the R₂ hydrocarbon groups can be straight orbranch-chained, can be of the same or different chain length, and cancontain alicyclic rings of 3 to 7 carbon atoms, such as cycloalkyl.Since the cyclopentanes are produced by hydrogenation, little if anyunsaturation, except possibly for aromatic double bonds, will remain inthe hydrocarbon substituents. In the definition of R₁ in the Formula Icompounds, as well as the compounds of Formulae II to VIII describedhereinafter, it will be understood that the alkyl groups may be the sameor different and straight or branch-chained.

These hydrocarbon substituted cyclopentanes have been found to provideexcellent lubricating characteristics which make them useful aslubricants in internal combustion engines and in other areas where goodlubricity is a requirement. The lubricants may comprise individualhydrocarbyl-substituted cyclopentanes or mixtures thereof. The compoundsprovide the appropriate specific gravity, refractive indices,viscosities, and low and high temperature characteristics which arerequired for an outstanding lubricant. In particular the lubricantsexhibit specific gravities ranging from about 0.835 to about 0.860;refractive indices ranging from about n_(D) ²⁵ C 1.450 to 1.40;viscosities at 100° C. (cSt) ranging from 2.0 to 20.0, at 40° C. (cST)ranging from 6.0 to 350, at 0° C. (cP) ranging from 200 to 13,000, andat -40° C. (cP), ranging from 1500 to 600,000. The viscosity indexranges from 45 to 200. The compositions also provide excellent lowtemperature pour points. Flash points range from 400° to 600° F. andfire points range from 450° to 650° F. with minimum loss to evaporationat these temperatures.

In the hydrocarbon substituted cyclopentane compositions describedabove, some compounds of the above formula which contain a single methylgroup substituent provide lubricants which have a lowered pour point ascompared to otherwise comparable cyclopentanes. This causes thecyclopentanes to be particularly useful in certain lubricatingenvironments.

A preferred group of hydrocarbon substituted cyclopentane lubricants arethose wherein x is an integer of 3 to 5, R₁ is methyl and z is 0 or 1,and R₂ is an alkyl group of 8 to 24 carbon atoms, and wherein x is aninteger of 2 to 4, R₁ is methyl and z is 0 or 1, and R₂ is an alkylgroup of 13 to 24 carbon atoms.

In further embodiments of the invention, the intermediatehydrocarbon-substituted cyclopentadienes and hydrocarbon substitutedcyclopentenes are also provided as lubricating compositions. Thesecompounds have lubricating characteristics including viscosities andpour points which make them useful in a variety of areas.

The lubricating compositions which comprise cyclopentadienes are of thefollowing formula: ##STR6## wherein z, R₁ and R₂ are as defined above inFormula I and x is an integer ranging from 1 to 6.

Also provided by the present invention are cyclopentene compositionswhich are useful as synthetic lubricants. These cyclopentenes may bedescribed by the following general formula: ##STR7## wherein R₁, R₂, zand x are as defined above.

There is also provided by the present invention partial syntheticlubricant compositions in which the hydrocarbon-substitutedcyclopentanes, the hydrocarbon-substituted cyclopentenes, or thehydrocarbon-substituted cyclopentadienes, used either alone or inadmixture, are mixed with a natural base fluid such as mineral oil toform the lubricant. Compositions of this type may contain about 10 to90% of any of the synthetic lubricants of this invention mixed with 90to 10% of a mineral oil base fluid. Compositions of this type showenhanced lubricant properties.

In a further embodiment of the invention, mixtures of thehydrocarbon-substituted cyclopentanes, the hydrocarbon-substitutedcyclopentenes, or the hydrocarbon-substituted cyclopentadienes, usedeither alone or in admixture, may be mixed with other syntheticlubricants such as poly-alpha-olefin, esters and polyol esters. Thesemixtures may include 10 to 90% of the synthetic hydrocarbon substitutedcyclopentanes, cyclopentenes, and/or cyclopentadienes of this invention,mixed with 90 to 10% of any other compatible synthetic lubricant.

In a still further embodiment of the invention, lubricating compositionsare provided which comprise mixtures of the hydrocarbon-substitutedcyclopentanes, hydrocarbon-substituted cyclopentenes, andhydrocarbon-substituted cyclopentadienes of this invention, the mixturesbeing in varying and all proportions. Mixtures of this type arise fromincomplete hydrogenation in production of the cyclopentanes from thecyclopentadienes as described hereinafter. This hydrogenated mixturewill comprise mixtures of these compounds which can be used as such as alubricating composition.

Preferred lubricating compositions according to the invention are thosecyclopentanes, cyclopentenes and cyclopentadienes which contain aplurality of R₂ hydrocarbyl groups, i.e., wherein x is 3 to 6. Even morepreferred are those compounds wherein the R₂ substituents arehydrocarbyl groups of different carbon chain length.

In a further embodiment of the invention, there are also provided agroup of novel hydrocarbyl substituted cyclopentanes which are of thefollowing formula: ##STR8## wherein in the above formula, R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, R₂ is individually and independently selected fromhydrocarbyl groups of 4 to 36 carbon atoms, preferably 8 to 36 carbonatoms, and more preferably 12 to 24 carbon atoms, and preferably arestraight or branch chained alkyl groups containing 4 to 36 carbon atoms,preferably 8 to 24 carbon atoms, which can contain alicyclic rings of 3to 7 carbon atoms, such as cycloalkyl, z is 0, 1, 2 or 3, and y is aninteger of from 2 to 6, provided that when at least two of the R₂ groupsare carbon chains of from about 4 to 10 carbon atoms, then the integer ymust be at least 3, and y+z cannot be greater than 6.

The hydrocarbon-substituted cyclopentanes of the present invention areprepared by hydrogenation of the corresponding hydrocarbon-substitutedcyclopentadienes by conventional hydrogenation techniques. Thehydrogenation reactions of this type are known in the art and generallycomprise reaction of the hydrocarbon-substituted cyclopentadieneintermediate or mixture of intermediates in the presence of ahydrogenation catalyst such as Raney nickel or palladium and in thepresence or absence of an organic solvent such as an aliphatichydrocarbon. In carrying out the hydrogenation reaction, the reactor ispressurized with hydrogen to a pressure which may range up to about 3000psi and heated in the range of 75° to 200° C. until the hydrogenation iscomplete as evidenced by cessation of hydrogen uptake. On removal of thecatalyst and solvent, the hydrogenated cyclopentane is recovered.

The hydrocarbon-substituted cyclopentadienes which serve as precursors,many of which are also novel compounds, may be characterized by thefollowing general formula: ##STR9## In the above formula, R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, R₂ is individually and independently selected fromhydrocarbon substituents of 4 to 36 carbon atoms, preferably 8 to 36carbon atoms, and more preferably 12 to 24 carbon atoms, preferablystraight or branch-chained alkyl groups, alkenyl groups, or alkynylgroups having from 4 to 36 carbon atoms, preferably 8 to 24 carbonatoms, which can contain alicyclic rings of 3 to 7 carbons such ascycloalkyl and/or aromatic rings of 6 to 12 carbon atoms, z is 0, 1, 2,or 3, x+z cannot be greater than 6, and x is an integer ranging from 1to 6. It is preferred that at least two of the R₂ groups contain from 8to 13 carbon atoms, and that x be an integer of 3 to 5.

A novel group of cyclopentadiene compounds are those of the formula:##STR10## wherein each R₁ is individually and independently selectedfrom alkyl groups of 1 to 4 carbon atoms, each R₂ is individually andindependently selected from hydrocarbyl groups of 8 to 36 carbon atoms,preferably 12 to 24 carbon atoms, attached to the ring through a primarycarbon, z is 0, 1, 2, or 3, and y is an integer of from 2 to 6, y+zcannot be greater than 6, and provided that when up to four of the R₂groups contain 4 to 11 carbon atoms, then y must be an integer of atleast 5. An important aspect of the alkylated cyclopentadiene compoundsis that the R₂ substituents are attached to the cyclopentane ringthrough a primary carbon.

An especially select group of novel cyclopentadienes are those of thestructure ##STR11## such that each of the R_(a) groups are individuallyand independently selected from hydrocarbyl groups of 1 to 4 carbonatoms and n=0 to 4, each of the R_(b) groups are individually andindependently selected from hydrocarbyl groups of 7 to 35 carbon atoms,preferably 8 to 24 carbon atoms, and m=0 to 6, and each of the (CHR_(c)R_(d)) groups are individually and independently selected fromhydrocarbyl groups of 8 to 36 carbon atoms, preferably 8 to 24 carbonatoms, in which R_(c) and R_(d) are individually and independentlyselected from hydrocarbyl groups of 1 to 24 carbon atoms, preferably 8to 24 carbon atoms, and p=0 to 5, provided that n+m+p is 2 to 6 and m+pis 2 to 6,

and provided that if n=0 and p=0 and there are no more than twodifferent R_(b) groups and no more than one R_(b) occurs more than once,and all the R_(b) have 10 or fewer carbon atoms, then m must be 5 or 6,

and provided that if n=0 and p=1 and both the R_(c) group and the R_(d)group have 10 or fewer carbon atoms and all the R_(b) groups are thesame and have 10 or fewer carbon atoms, then m must be 4 or 5,

and provided that if n=1 and p=0 and all the R_(b) groups are the sameand have 10 or fewer carbon atoms, then m must be 4 or 5,

and provided that if n=0 and m=0 and there are no more than twodifferent (CHR_(c) R_(d)) groups and no more than one (CHR_(c) R_(d))occurs more than once and all the R_(c) groups and R_(d) groups have 10or fewer carbon atoms, then p must be 4 or 5,

and provided that if n=0 and m=1 and the R_(b) group has 10 or fewercarbons, and all the R_(c) groups are the same and have 10 or fewercarbon atoms and all the R_(d) groups are the same and have 10 or fewercarbon atoms, then p must be 3 or 4,

and provided that if n=1 and m=0 and all the (CHR_(c) R_(d)) groups arethe same and the R_(c) and R_(d) groups both have 10 or fewer carbonatoms, then p must be 3 or 4.

The intermediate hydrocarbon-substituted cyclopentenes, most of whichare also novel compounds, may be characterized by the following generalformula: ##STR12## In the above formula, R₁ is individually andindependently selected from alkyl groups of 1 to 4 carbon atoms, R₂ isindividually and independently selected from hydrocarbon substituents of4 to 36 carbon atoms, preferably 8 to 36 carbon atoms, more preferably12 to 24 carbon atoms, preferably straight or branch-chained alkylgroups having from 4 to 36 carbon atoms, preferably 8 to 24 carbonatoms, which can contain alicyclic rings of 3 to 7 carbons such ascycloalkyl, and/or aromatic rings of 6 to 12 carbons, z is 0, 1, 2 or 3,and x is an integer ranging from 1 to 6, and x+z cannot be greater than6. It is preferred that at least two of the R₂ groups contain from 4 to10 carbon atoms, and that x be an integer of 3 to 5. A preferred groupof compounds includes those wherein the R₂ groups contain from 8 to 12carbon atoms and x is 3 to 5.

A novel group of cyclopentene compounds are those of the formula:##STR13## wherein z, R₁ and R₂ are as defined above, and y is an integerof 2 to 6, provided that when at least two of the R₂ groups contain from4 to 10 carbon atoms then y is an integer of at least 3. In aparticularly preferred group, when R₂ is an alkyl group which containsfrom 4 to 10 carbon atoms, then the integer x is 3, 4 or 5, the latterparticularly representing a group of novel cyclopentene intermediates.

In the cyclopentanes, cyclopentenes and cyclopentadienes of theinvention, the total number of carbon atoms in the R₂ substituentsshould preferably not exceed about 80.

Preferred compounds or mixtures of compounds according to the inventioninclude cyclopentane, cyclopentadiene, and cyclopentene lubricantswhich, with reference to Formulae I, II, and III, may be defined asfollows:

(1)

z=0;

x=3 or 4;

R₂ =C₈ and/or C₁₀ alkyl hydrocarbon.

(2)

z=0;

x=3 or 4;

R₂ =C₉ and/or C₁₀ and/or C₁₁ alkyl hydrocarbon.

(3)

z=0;

x=3 or 4;

R₂ =C₁₂ and/or C₁₃ alkyl hydrocarbon.

(4)

z=0;

x=2 or 3;

R₂ =2-octyl-1-dodecyl.

Particularly preferred specific classes of compounds and specificcompounds or mixtures which are also useful as lubricants include thefollowing:

Cyclopentanes

Tri-n-octyl cyclopentane

Tetra-n-octyl cyclopentane

Penta-n-octyl cyclopentane

Tri-n-nonyl cyclopentane

Tetra-n-nonyl cyclopentane

Penta-n-nonyl cyclopentane

Tri-n-decyl cyclopentane

Tetra-n-decyl cyclopentane

Penta-n-decyl cyclopentane

Tri-n-undecyl cyclopentane

Tetra-n-undecyl cyclopentane

Penta-n-undecyl cyclopentane

Tri-n-dodecyl cyclopentane

Tetra-n-dodecyl cyclopentane

Penta-n-dodecyl cyclopentane

Tri-2-ethylhexyl cyclopentane

Tetra-2-ethylhexyl cyclopentane

Di-n-octyl, n-decyl cyclopentane

n-octyl, di-n-decyl cyclopentane

Trioctyl, n-decyl cyclopentane

Di-n-octyl, di-n-decyl cyclopentane

n-octyl, tri-n-decyl cyclopentane

Tri-n-tridecyl cyclopentane

Tetra-n-tridecyl cyclopentane

Penta-n-tridecyl cyclopentane

Di-(2-octyl-1-dodecyl)cyclopentane

Tri-(2-octyl-1-dodecyl)cyclopentane

Tetra-(2-octyl-1-dodecyl)cyclopentane

Cyclopentenes

Tri-n-octyl cyclopentene

Tetra-n-octyl cyclopentene

Penta-n-octyl cyclopentene

Tri-n-nonyl cyclopentene

Tetra-n-nonyl cyclopentene

Penta-n-nonyl cyclopentene

Tri-n-decyl cyclopentene

Tetra-n-decyl cyclopentene

Penta-n-decyl cyclopentene

Tri-n-undecyl cyclopentene

Tetra-n-undecyl cyclopentene

Penta-n-undecyl cyclopentene

Tri-n-dodecyl cyclopentene

Tetra-n-dodecyl cyclopentene

Penta-n-dodecyl cyclopentene

Tri-2-ethylhexyl cyclopentene

Tetra-2-ethylhexyl cyclopentene

Di-n-octyl, n-decyl cyclopentene

n-octyl, di-n-decyl cyclopentene

Trioctyl, n-decyl cyclopentene

Di-n-octyl, di-n-decyl cyclopentene

n-octyl, tri-n-decyl cyclopentene

Tri-n-tridecyl cyclopentene

Tetra-n-tridecyl cyclopentene

Penta-n-tridecyl cyclopentene

Di-(2-octyl-1-dodecyl)cyclopentene

Tri-(2-octyl-1-dodecyl)cyclopentene

Tetra-(2-octyl-1-dodecyl)cyclopentene

Cyclopentadienes

Tri-dodecyl cyclopentadiene

Tetra-dodecyl cyclopentadiene

Penta-dodecyl cyclopentadiene

Penta-n-butyl cyclopentadiene

Penta-n-octyl cyclopentadiene

Penta-n-nonyl cyclopentadiene

Penta-n-decyl cyclopentadiene

Di-n-octyl, n-decyl cyclopentadiene

n-octyl, di-n-decyl cyclopentadiene

Trioctyl, n-decyl cyclopentadiene

Di-n-octyl, di-n-decyl cyclopentadiene

n-octyl, tri-n-decyl cyclopentadiene

Tri-n-tridecyl cyclopentadiene

Tetra-n-tridecyl cyclopentadiene

Penta-n-tridecyl cyclopentadiene

Di-(2-octyl-1-dodecyl)cyclopentadiene

Tri-(2-octyl-1-dodecyl)cyclopentadiene

Tetra-(2-octyl-1-dodecyl)cyclopentadiene

Di-n-octyl-Tri-n-decyl cyclopentadiene

Tri-n-octyl-Di-n-decyl cyclopentadiene

Methyl-n-octyl-n-decyl cyclopentadiene

Methyl-Di-n-octyl-n-decyl cyclopentadiene

Methyl-Tri-n-octyl-n-decyl cyclopentadiene

Methyl-n-octyl-di-n-decyl cyclopentadiene

Methyl-n-octyl-tri-n-decyl cyclopentadiene

Dimethyl-n-octyl-n-decyl cyclopentadiene

Dimethyl-di-n-octyl-n-decyl cyclopentadiene

Dimethyl-n-octyl-di-n-decyl cyclopentadiene

n-nonyl-n-decyl-n-undecyl cyclopentadiene

Di-n-nonyl-n-decyl-n-undecyl cyclopentadiene

n-nonyl-di-n-decyl-n-undecyl cyclopentadiene

n-nonyl-n-decyl-di-n-undecyl cyclopentadiene.

The hydrocarbyl substituted cyclopentadiene intermediates of theinvention are prepared using a hydrocarbylating or phase transferpreparation method or an alcohol preparation method. In the phasetransfer method, cyclopentadiene or substituted cyclopentadiene and analkylating agent such as an alkyl halide or mixture of alkyl halides areadded to a reaction vessel containing an alkaline aqueous solution andfurther containing a phase transfer catalytic agent. The alkylatingagent is used in a molar excess depending on the amount of alkylsubstitution desired. The preferred alkylating agent is an alkyl halideof the formula, R₂ Y wherein R₂ is as described above and Y is a leavinggroup, preferably Cl or Br, and the process is described herein withreference to this reaction. It is preferred that about 3 to 6 moles ofalkyl halide should be used per mole of cyclopentadiene. The alkalineaqueous solution will comprise sodium hydroxide or potassium hydroxidein preferred embodiments. The mixture of cyclopentadiene, alkyl halide,catalyst and alkali is permitted to react in aqueous solution withvigorous stirring for a period of from about 1/2 to 10 hours. Oncompletion of the reaction, and cessation of agitation, two phases willform, an organic phase and a water phase. The product will be containedin the organic phase and may be recovered by conventional methods as byseparation of phases and recovery.

It is sometimes desirable to add an organic solvent or water or both tofacilitate separation of the two phases. In a preferred procedure, theorganic layer is removed and any excess alkyl halide and/or solventremoved to provide the alkylated cyclopentadiene which can be used forconversion to the cyclopentane without further purification. This is asingle step reaction which provides good yields of the substitutedcyclopentadiene.

In conducting the hydrocarbylation reaction by the phase transfermethod, the preferred temperature range is from about -20° to 120° C.with a residence time or reaction time of from 1/2 hour up to 3 days.The molar ratio of alkyl halide to cyclopentadiene should range fromabout 1:1 up to about 20:1. The ratio of alkali metal hydroxide tocyclopentadiene reactant in this reaction may range from 1:1 up to 50:1.

Suitable phase transfer catalysts include n-alkyl (C₁₂ -C₁₆)dimethylbenzylammonium chloride, sold commercially as Hyamine 3500,triethylbenzylammonium chloride, sold commercially as TEBAC, a mixtureof methyl trialkyl (C₈ -C₁₀) ammonium chlorides, sold commercially asAdogen® 464, polyethylene glycols and polyethers.

In a separate method for preparation of the hydrocarbon-substitutedcyclopentadienes, an alcohol or mixture of alcohols of the formula R₂ OHwherein R₂ is as described above, is combined with a basic catalyst suchas an alkali metal hydroxide or alkoxide in a reaction vessel. Thealcohol reactant or mixture of alcohols is a primary or secondaryalcohol and is used in sufficient amounts to provide a molar excess ofabout 3 to 6 moles. It is preferred to use a mixture of alcohols as thereactant since alkylated compounds of different side chain length can beproduced. The use of mixtures of alcohols to alkylate cyclopentadienesgreatly enhances the utility of the process. In particular, propertiesof products produced by alkylation of cyclopentadienes with a mixture oftwo or more alcohols can be continuously and conveniently varied betweenthose of the products produced by the separate alkylation ofcyclopentadienes with each of the two pure alcohols. The cyclopentadieneor hydrocarbon-substituted cyclopentadiene is then added to the reactionvessel at room temperature or a temperature as high as the refluxtemperature of the mixture, which would be at about the boilingtemperature of the alcohol(s) being used. Alternatively, a portion ofthe cyclopentadiene may be mixed with the alcohol and alkali in thereactor and the remaining cyclopentadiene added to the reaction mixtureover a period of time as the reaction proceeds. An inert solvent mayalso be included if necessary depending on the alcohol reactants.Further, the reaction may be carried out in a closed container so thathigher temperatures in excess of 180°, and up to 260° C. can be reachedusing lower boiling alcohols. As the reaction proceeds, water will beproduced and is removed as it is formed. This is an important feature ofthe invention since it appears to drive the reaction to completion andincrease yields substantially. On completion of the reaction, themixture is allowed to cool and then mixed with water or poured onto iceand two layers allowed to separate. The organic and aqueous layers areseparated using an organic solvent to aid the separation if necessary.After removal of excess alcohol and any solvent from the organic layer,the polyalkyl cyclopentadiene is recovered.

In an alternative work-up procedure, the reaction mixture may befiltered. The alcohol may be separated by distillation before or afterfiltration.

It was unexpected that high yields of polyalkylated products fromalcohols, including long chain alcohols, could be obtained from thisreaction without the use of high pressure.

In conducting the hydrocarbylation by the alcohol method, minor sideproducts may be formed. For example, the acid corresponding to thealcohol and a dimeric alcohol may also be formed. The careful exclusionof oxygen and careful adjustment of the alcohol to base ratios aid insuppression of the formation of these byproducts. If secondary alcoholsare used, the byproducts are less significant.

The alcohol alkylation is preferably carried out in the temperaturerange of 180°-300° C. for a reaction time which may range from 10minutes to 3 days. The mole ratio of alcohol to cyclopentadiene mayrange from 1:1 up to 50:1 and the ratio of alkali metal hydroxide oralkoxide to cyclopentadiene reactant may range from 0.1:1 up to 10:1.

The precursor cyclopentadienes to be reacted by the phase transfermethod or alcohol method are preferably those set forth in Formula Vabove except that in such case, x can be 0, and x+z must be 0, 1, 2, 3,4 or 5 in the phase transfer method, and x+z must be 0, 1, 2, 3 or 4 inthe alcohol method. Also, no two hydrocarbon substituents can begerminal. For example the R₁ and/or R₂ hydrocarbyl groups could be addedstepwise depending on the amount of hydrocarbylating agent used. Thefinal products and precursor compounds as described are considered to beinclusive of all such compounds.

The cyclopentene intermediates of this invention are produced by partialor incomplete hydrogenation of the cyclopentadienes when preparing thecyclopentanes. This hydrogenation reaction if carried to completion willproduce the cyclopentanes described above. However, incompletehydrogenation will result in production of at least some cyclopentenesand usually a mixture of the hydrocarbon substituted cyclopentenes andcyclopentanes. Some starting cyclopentadienes which are not hydrogenatedmay also remain in the mixture. Thus, the hydrogenation reaction canproduce a variety of mixtures of products as well as the cyclopentenesand the cyclopentanes of the invention.

The following examples are presented to illustrate the invention but theinvention is not to be considered as limited thereto. In the examplesand throughout the specification, parts are by weight unless otherwiseindicated.

EXAMPLE 1 Preparation of Di(n-octyl)cyclopentadienes (Phase TransferMethod)

Cyclopentadiene (99 g, 1.5 moles), and n-octyl bromide (476 g, 3.2moles), were added to a 5-liter reaction flask, containing an aqueous 56percent potassium hydroxide solution (1950 ml, 30 moles KOH) and acatalytic amount of Adogen® 464 (25 g), cooled in an ice bath. Themixture was stirred vigorously for 30 minutes in the ice bath, then thebath was removed. The mixture was stirred for an additional 3 hours,while warming to room temperature. The layers were separated, water andpentane being added to facilitate workup, and the organic phase waswashed with water until neutral. The organic layer was dried over MgSO₄and the pentane removed in vacuo, affording 372 g crude yield.

Gas chromatographic analysis provided the following analysis (86.5%total yield):

mono(n-octyl)cyclopentadienes 15.2%, 56.5 g, 0.317 moles (21.1% yield)

di(n-octyl)cyclopentadienes 75.7%, 281.6 g, 0.971 moles (64.7% yield);

tri(n-octyl)cyclopentadienes 1.1%, 4.1 g, 0.010 moles (0.6% yield).

EXAMPLE 2 Preparation of tri/tetra(n-decyl)cyclopentadienes (PhaseTransfer Method)

Cyclopentadiene (23 g, 0.35 moles), and n-decyl bromide (300 g, 1.36moles), were added to a 2-liter reaction flask containing an aqueous 56percent potassium hydroxide solution (500 ml, 7.5 moles KOH) and acatalytic amount of Adogen® 464 (13 g), in a water bath at roomtemperature. The mixture was vigorously stirred for one hour thenheated, with continuing stirring for 41/2 hours at 100° C. Aftercooling, the layers were separated, water and heptane added tofacilitate workup, and the organic phase was washed with water untilneutral. The organic phase was dried over MgSO₄ and the solvent removedin vacuo, affording 247 g crude yield. Unreacted n-decyl bromide (40 g,0.18 mole) was distilled off to give a pot residue (200 g) of product.

Gas chromatographic analysis provided the following analysis (98.6%total yield):

di(n-decyl)ether 3.4%, 6.8 g, 0.023 moles;

di(n-decyl)cyclopentadienes 0.8%, 1.6 g, 0.005 moles (1.4% yield);tri(n-decyl)cyclopentadienes 41.2%, 82.4 g, 0.170 moles (48.6% yield);

tetra(n-decyl)cyclopentadienes 53.3%, 106.6 g, 0.170 moles (48.6%yield).

EXAMPLE 3 Preparation of Isodecylcyclopentanes (Alcohol method)

Isodecanol (420 g, 2.65 moles) and solid potassium hydroxide (87%, 10.3g, 0.16 moles KOH) were mixed in a 1-liter reaction flask fitted with amechanical stirrer, a dropping funnel, a Dean-Stark trap with condenser,a thermometer and a serum capped sampling port. Prior to heating, aportion of the dicyclopentadiene (6.6 g, 0.05 moles) was added to thereaction mixture. The flask was then heated to 200° C. After water begancollecting in the Dean-Stark trap, the remaining dicyclopentadiene (28.4g, 0.22 moles) was added dropwise over a 1.5 hour period. The reactionmixture was heated for 4 hours after the completion of thedicyclopentadiene addition. The temperature rose to 245° C. over thecourse of the reaction. After cooling, the reaction mixture was pouredinto water. Hexane was added to facilitate workup. The layers wereseparated. The aqueous layer was saved for further workup. The organicphase was washed with water until neutral. The organics were dried overMgSO₄ and the solvent removed in vacuo. The organic concentrate wascarried through the hydrogenation affording 387 g.

Gas chromatographic analysis provided the following analysis (80% totalyield):

isodecanol 25.4%, 98.3 g, 0.621 moles;

isoeicosanol 2.9%, 11.2 g, 0.0380 moles;

tri(isodecyl)cyclopentanes 7.0%, 27.1 g, 0.056 moles (11% yield);

tetra(isodecyl)cyclopentanes 48.1%, 186.1 g, 0.297 moles (56% yield);

penta(isodecyl) cyclopentanes 13.0%, 50.3 g, 0.066 moles (13% yield).

The aqueous layer was acidified with hydrochloric acid and extractedwith ether. The layers were separated and the organic layer washed withwater until neutral. The organics were dried over MgSO₄ and the solventremoved in vacuo, affording isodecanoic acid (23.4 g, 0.136 moles). Ofthe 2.65 moles of isodecanol used, 2.52 moles (95%) are accounted for.

EXAMPLE 4 Hydrogenation of tri(n-decyl)cyclopentadienes

A 4-liter autoclave was charged with the crude alkylcyclopentadienes(159 g; di(n-decyl)cyclopentadienes, 34.7 g, 21.8%;tri(n-decyl)cyclopentadienes, 117.2 g, 73.7%; andtetra(n-decyl)cyclopentadienes 2.2 g, 1.4%), (prepared as in Example 2)10% palladium on activated carbon (4 gms), and heptane (500 ml) tofacilitate stirring. The vessel was pressurized to 500 psi of hydrogenand heated at 125° C. for 19 hours with stirring. After cooling, thevessel pressure was 350 psi. The catalyst was filtered and the solventremoved in vacuo affording 150 g of clear colorless oil with a brominenumber of zero.

EXAMPLE 5

Using the procedures of Examples 1, 2 and 3, the cyclopentadienederivatives set forth in the following Table 1 were prepared. The tableindicates the preparative method used.

                  TABLE 1                                                         ______________________________________                                        CYCLOPENTADIENE DERIVATIVE                                                     ##STR14##                                                                                         x =                                                      R.sub.2  Formula  Class.sup.a                                                                           Method.sup.b                                                                         2   3   4   5   6                            ______________________________________                                        n-butyl  C.sub.4 H.sub.9                                                                        1°                                                                             P      x   x   x   x   x                            n-hexyl  C.sub.6 H.sub.13                                                                       1°                                                                             P      x   x   x   x   x                            n-octyl  C.sub.8 H.sub.17                                                                       1°                                                                             P, A   x   x   x   x                                n-decyl  C.sub.10 H.sub.21                                                                      1°                                                                             P, A   x   x   x   x                                n-dodecyl                                                                              C.sub.12 H.sub.25                                                                      1°                                                                             P, A   x   x   x   x                                n-tetradecyl                                                                           C.sub.14 H.sub.29                                                                      1°                                                                             P      x   x   x                                    isodecyl C.sub.10 H.sub.21                                                                      1°                                                                             A      x   x   x   x                                isotridecyl                                                                            C.sub.13 H.sub.27                                                                      1°                                                                             A      x   x   x   x                                2-ethyl- C.sub.8 H.sub.17                                                                       1°                                                                             P, A   x   x   x                                    1-hexyl                                                                       2-octyl- C.sub.20 H.sub.41                                                                      1°                                                                             A      x   x                                        1-dodecyl                                                                     2-decyl-1-                                                                             C.sub.24 H.sub.49                                                                      1°                                                                             A      x   x                                        tetradecyl                                                                    2-octyl  C.sub.8 H.sub.17                                                                       2°                                                                             P, A   x   x                                        t-butyl  C.sub.4 H.sub.9                                                                        3°                                                                             P      x   x                                        ______________________________________                                         .sup.a 1° = primary alkyl; 2° = secondary alkyl; 3°      tertiary alkyl                                                                .sup.b P = Phase Transfer method; A = Alcohol method                     

EXAMPLE 6

Using the procedures of Examples 1, 2 and 3, the methylcyclopentadienesset forth in the following Table 2 were prepared. The preparative methodis indicated.

                  TABLE 2                                                         ______________________________________                                        METHYLCYCLOPENTADIENE                                                          ##STR15##                                                                                           x =                                                    R.sub.2  Formula   Class.sup.a                                                                            Method.sup.b                                                                         2   3   4   5                              ______________________________________                                        n-octyl  C.sub.8 H.sub.17                                                                        1°                                                                              A      x   x   x                                  n-decyl  C.sub.10 H.sub.21                                                                       1°                                                                              A, P   x   x   x                                  n-dodecyl                                                                              C.sub.12 H.sub.25                                                                       1°                                                                              A      x   x   x                                  isodecyl C.sub.10 H.sub.21                                                                       1°                                                                              A      x   x   x                                  ______________________________________                                         .sup.a 1° = primary alkyl                                              .sup.b P = Phase Transfer method; A = Alcohol method                     

EXAMPLE 7

Using the hydrogenation procedures of Example 4, the alkyl substitutedcyclopentanes of Table 3 were prepared. The column indicating "Class"designates a straight or branch chained substituent.

                  TABLE 3                                                         ______________________________________                                        CYCLOPENTANE DERIVATIVES                                                       ##STR16##                                                                                          x =                                                     R.sub.2      Formula   Class.sup.a                                                                            2   3   4   5                                 ______________________________________                                        n-octyl      C.sub.8 H.sub.17                                                                        1°                                                                              x   x   x   x                                 n-decyl      C.sub.10 H.sub.21                                                                       1°                                                                              x   x   x   x                                 n-dodecyl    C.sub.12 H.sub.25                                                                       1°                                                                              x   x   x   x                                 isodecyl     C.sub.10 H.sub.21                                                                       1°                                                                              x   x   x   x                                 isotridecyl  C.sub.13 H.sub.27                                                                       1°                                                                              x   x   x   x                                 2-ethyl-1-hexyl                                                                            C.sub.8 H.sub.17                                                                        1°                                                                              x   x   x                                     2-octyl-1-dodecyl                                                                          C.sub.20 H.sub.41                                                                       1°                                                                              x   x                                         2-decyl-1-tetradecyl                                                                       C.sub.24 H.sub.49                                                                       1°                                                                              x   x                                         2-octyl      C.sub.8 H.sub.17                                                                        2°                                                                              x   x                                         ______________________________________                                         .sup.a 1° = primary alcohol; 2° = secondary alcohol        

EXAMPLE 8

Using the hydrogenation procedures of Example 4, the substitutedmethylcyclopentanes of Table 4 were prepared. The column indicating"Class" designates a straight or branch chained substituent.

                  TABLE 4                                                         ______________________________________                                        METHYLCYCLOPENTANE DERIVATIVES                                                 ##STR17##                                                                                          x =                                                     R.sub.2  FORMULA     CLASS      2    3    4                                   ______________________________________                                        n-octyl  C.sub.8 H.sub.17                                                                          1°  x    x    x                                   n-decyl  C.sub.10 H.sub.21                                                                         1°  x    x    x                                   n-dodecyl                                                                              C.sub.12 H.sub.25                                                                         1°  x    x    x                                   isodecyl C.sub.10 H.sub.21                                                                         1°  x    x    x                                   ______________________________________                                    

EXAMPLE 9--CHEMICAL IDENTIFICATION

Chemical characterization of alkylcyclopentadienes andalkylcyclopentanes was by infrared spectroscopy (IR), nuclear magneticresonance spectrometry (NMR) and gas chromatography (GC), especially inconjunction with mass spectrometry (GC-MS). A few examples weremeticulously examined and structures of products determined and thenquantitative analysis and further identification was made by analogy tothese carefully characterized samples.

Interpretation of Spectroscopic Data

Mass Spectrometry

Alkylcyclopentadienes (see Table 5 following)--A detailed analysis ofn-butyl cyclopentadienes showed that the parent peak was prominentenough to be recognizable. Common fragments were P-43 (minus n-propyl),P-57 (minus n-butyl), P-98 (minus propene and butene), P-99 (minusn-propyl and n-butene) and 57 (n-butyl). Other cyclopentadienes alsogave parent peaks prominent enough to allow assignment to be made onthat basis alone.

Alkylcyclopentanes--Mass spectra are very similar to other saturatedhydrocarbons except that the parent is C_(n) H_(2n).

Infrared Spectroscopy

Alkylcyclopentanes (See Table 6 following)--The IR spectra areindistinguishable from other saturated hydrocarbons with alkylcomponents; e.g., hydrogenated 1-decene oligomers. Bands are at 2960cm⁻¹, 2850 cm⁻¹ (H-C(sp³) stretch); 1460 cm⁻¹, 1375 cm⁻¹, (H-C(sp³)bend) and 720 cm⁻¹ (--(CH₂)_(x) --rock, x>4).

Alkylcyclopentadienes (See Table 6)--In addition to the bands found inthe alkylcyclopentanes, bands for unsaturation are found at 3050 cm⁻¹(H-C(sp²) stretch), 1650 and 1620 (C═C stretch), 970 and 890 (H-C(sp²)bend).

Nuclear Magnetic Resonance Spectrometry

Alkylcyclopentanes--Both ¹ H and ¹³ C NMR Spectra are dominated byn-alkyl resonances: (1) ¹ H NMR, CH₃ at 0.9 ppm, CH₂ at 1.3 ppm, CH at1.5; (2) ¹³ C NMR, CH₃ -- 14.2 ppm, CH₂ 's at 22.8 ppm, 29.7 ppm, 32.0ppm and CH's clustered about 40 ppm.

Alkylcyclopentadienes--In addition to the resonance ofalkylcyclopentanes due to the alkyl groups, unsaturation leads toresonances at 5.80 and 6.20 ppm in the ¹ H spectrum for protons on sp²carbon and 2.35 and 2.8 for allylic and bis-allylic CH₂ 's respectively.Similarly, resonances due to unsaturation are observed in the 150.0 to110.00 ppm region for sp² carbons and 45.0 to 35.0 ppm region forallylic carbons in the ¹³ C spectra of alkylcyclopentadienes.

                                      TABLE 5                                     __________________________________________________________________________    Mass Spectral Data for Alkyl Cyclopentadienes                                 GC - Mass Spec of C.sub.5 (R.sub.2).sub.x H.sub.6-x, R.sub.2 ═            n-butyl                                                                       Retention                                                                            INTENSITY (% OF BASE PEAK)                                               Time P (Parent)                                                                          P-43                                                                              P-56                                                                              P-57                                                                              P-71 P-85 P-88 P-99 57                               X (Minutes)                                                                          M.sup.+                                                                             --C.sub.3 H.sub.7                                                                 --C.sub.4 H.sub.8                                                                 --C.sub.4 H.sub.9                                                                 --C.sub.5 H.sub.11                                                                 --C.sub.6 H.sub.13                                                                 --C.sub.7 H.sub.14                                                                 --C.sub.7 H.sub.14                                                                 C.sub.4 H.sub.9                  __________________________________________________________________________    2 20.4 24    45   0  42  24   95   63   100  40                               3 29.4 18    53  55  18  53   19   40   100  60                               3 29.5 18    33   3  16  62   17   27   100  53                               3 32.1 27    100  2  12  10   42   40    42  24                               4 35.8  9    52   3  10  0     8   29    27  100                              4 36.1 22    100 12  23  2    12   47    50  88                               4 36.5 25    100 10  25  2    12   47    38  86                               4 37.2 17    22  88  18  1     7   47   100  62                               4 37.9 30    100  8  20  3    12   35    42  56                               4 38.3  7    <1  18  100 0     1   <1    3   16                               5 40.8 32    79  23  19  0     5   14    38  100                              5 41.4 45    100 23  19  1     6   27    35  67                               5 42.2  5    <1  26  100 0     0    2    2   17                               6 45.5 100   89  32  30  0     2   10    38  37                               __________________________________________________________________________

                  TABLE 6                                                         ______________________________________                                        Infrared Spectra of Representative Alkylcyclopentadienes                      and Alkylcyclopentanes                                                        Di(n-decyl)cyclopentadienes and Di(n-decyl)cyclopentanes.                     Frequency, ν                                                                ##STR18##                                                                                 ##STR19##     Assignment                                         ______________________________________                                        3044 cm.sup.-1            sp.sup.2 CH stretch                                 2960        2960          sp.sup.3 CH stretch                                 2850        2850          sp.sup.3 CH stretch                                 1653                      cc stretch                                          1622                      cc stretch                                          1560                      cc stretch                                          1465        1465          CH.sub.2 bending                                    1375        1375          CH.sub.3 bending                                    968                       sp.sup.2 CH bend                                    891                       sp.sup.2 CH bend                                    721         721           (CH.sub.2).sub.x x > 4,                                                       rocking                                             ______________________________________                                    

EXAMPLE 10

To evaluate the alkyl cyclopentanes for lubricating properties, testswere carried out to measure physical properties which are relevant touse as a synthetic lubricant. Set forth in the following Table 7 arespecific gravity values of the indicated cyclopentanes, in Table 8 areset forth refractive index values of the indicated cyclopentanes, inTable 9 are set forth viscometric properties of the indicatedalkylcyclopentanes; in Table 10 are low temperature properties of theindicated alkylcyclopentanes; and set forth in Table 11 are hightemperature properties of the indicated alkylcyclopentanes.

                  TABLE 7                                                         ______________________________________                                        Specific Gravity of Representative Alkylcyclopentanes                          ##STR20##                                                                                  X =                                                             Sample #                                                                              R.sub.1                                                                             R.sub.2   2   3     4     5    S.G.                             ______________________________________                                        1       H     (n-decyl) --  100%  --    --   0.8368                           2       H     (n-octyl) --  --    100%  --   0.8368                           3       H     (n-decyl) --   20%   70%  10%  0.8430                           4       H     (n-decyl) --  --     67%  33%  0.8450                           5       H     (n-dodecyl)                                                                             --   40%   60%  --   0.8509                           ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Refractive Indexes of Representative Alkylcyclopentanes                        ##STR21##                                                                    Sam-                                                                          ple                 X =                                                       #    R.sub.1   R.sub.2  2   3     4     5    n.sub.D.sup.25°           ______________________________________                                                                                     C.                               1    H         n-octyl  --  100%  --    --   1.4573                           2    H         n-decyl  --  100%  --    --   1.4604                           3    H/Me=1/1  n-decyl  --  100%  --    --   1.4612                           4    H         n-octyl  --  --    100%  --   1.4612                           5    Me        n-octyl  --   40%   60%  --   1.4630                           6    H         n-decyl  --   30%   65%   5%  1.4636                           7    H         n-decyl  --  --     67%  33%  1.4654                           8    H         n-dodecyl                                                                              --   40%   60%       1.4647                           9    H         isodecyl                      1.4672                           ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________    Viscometric Properties of Representative Alkylcyclopentanes                    ##STR22##                                                                                          X =             Viscosity                                                                     100° C.                                                                    40° C.                                                                      0° C.                                                                       -40° C.                                                                     Viscosity            Sample #                                                                            R.sub.1                                                                              R.sub.2  2   3   4   5   (cSt).sup.a                                                                       (cSt).sup.a                                                                        (cP).sup.b                                                                         (cP).sup.b                                                                         Index                __________________________________________________________________________    1     H      n-octyl  100%                                                                              --  --  --  2.18                                                                              6.49           158                  2     H      n-decyl  100%                                                                              --  --  --  3.03                                                                              10.37          161                  3     H      n-dodecyl                                                                              100%                                                                              --  --  --  4.13                                                                              15.64          178                  4     H      n-octyl  --  100%                                                                              --  --  3.68                                                                              15.58                                                                              --    1676                                                                              124                  5     H      n-decyl  --  100%                                                                              --  --  5.15                                                                              23.99          151                  6     Me     n-decyl  --  100%                                                                              --  --  5.82                                                                              29.64                                                                                247                                                                               6,886                                                                             143                  7     H/Me = n-decyl  --  100%                                                                              --  --  5.60                                                                              27.82                                                                                242                                                                               5,800                                                                             145                  8     H      n-dodecyl                                                                              --  100%                                                                              --  --  6.99                                                                              35.26          150                  9     H      n-octyl  --  --  100%                                                                              --  5.99                                                                              33.43                                                                                363                                                                               15,386                                                                            125                  10    H      n-decyl  --  --  100%                                                                              --  7.99                                                                              46.70                                                                                602                                                                               14,958                                                                            143                  11    H      isodecyl --  --  X   --  11.68                                                                             119.60                                                                              2,584                                                                             556,000                                                                             83                  12    H      isotridecyl                                                                            --  --  X   --  20.09                                                                             310.22                                                                             12,700                                                                             solid                                                                               71                  13    H      2-octyldodecyl                                                                          15%                                                                               85%                                                                              --  --  15.10                                                                             114.97                                                                              1,500                                                                             224,000                                                                            136                  14    H      2-decyltetradecyl                                                                       40%                                                                               60%                                                                              --  --  16.34                                                                             118.51         148                  15    H      n-dodecyl                                                                              --  --   50%                                                                              50% 11.91                                                                             83.19          153                  __________________________________________________________________________     .sup.a ASTM D445                                                              .sup.b ASTM D3829                                                             .sup.c ASTM D2270                                                        

                                      TABLE 10                                    __________________________________________________________________________    Low Temperature Properties of Representative Alkylcyclopentanes                ##STR23##                                                                                         X =             MRV.sup.a,cp                                                                        CCS.sup.b,cp                                                                        Pour.sup.c                   Sample #                                                                            R.sub.1                                                                              R.sub.2 2   3   4   5   -30° C.                                                                      -25° C.                                                                      Point,                       __________________________________________________________________________                                                     °F.                   1     H      n-octyl 100%                                                                              --  --  --               -10                         2     H      n-decyl 100%                                                                              --  --  --               +40                         3     H      n-dodecyl                                                                             100%                                                                              --  --  --               +70                         4     H      n-octyl --  100%                                                                              --  --    720 <500  <-70°                 5     H      n-decyl --  100%                                                                              --  --               -20                         6     H      n-dodecyl                                                                             --  100%                                                                              --  --               +15                         7     H      n-octyl --  --  100%                                                                              --  3,662 1,640 <-55                         8     H      n-decyl --  --  100%                                                                              --  4,498 2,385 <-75                         9     H      n-dodecyl                                                                             --   40%                                                                               60%                                                                              --                +5                         10    H      n-decyl --   20%                                                                               70%                                                                              10% 3,375 2,263 <-65                         11    Me     n-octyl --   40%                                                                               60%                                                                              --  2,171 1,200 <-60°                 12    Me     n-decyl --   67%                                                                               33%                                                                              --  2,549 1,850 <-50°                 13    H      n-decyl --  --   67%                                                                              33% 5,743 3,500 <-50°                 14    Me     n-decyl --  100%                                                                              --  --  2,931 1,350 <-60°                 15    H/Me = 1:1                                                                           n-decyl --  100%                                                                              --  --  2,681 1,186 <-50°                 16    H      2-ethylhexyl                                                                          --   95%                                                                               5% --              <-55                         17    H      2-octyl  15%                                                                               85%                                                                              --  --              <-65                         18    H      isodecyl                                                                              --  --  X   --  103,000                                                                             >15,000                                                                              -30                         19    H      isotridecyl                                                                           --  --  X   --  369,000                                                                             solid  -15                         20    H      2-octyldodecyl                                                                         15%                                                                               85%                                                                              --  --  20,500                                                                              11,700                                                                               -60                         __________________________________________________________________________     .sup.a MRV = Borderline pumping test by minirotary viscometer (ASTM D3829     .sup.b CCS = Cold cranking simulator (ASTM D2062)                             .sup.c Pour Point (ASTM D97)                                             

                                      TABLE 11                                    __________________________________________________________________________    High Temperature Properties of Alkylcyclopentanes                              ##STR24##                                                                                  X =         Flash.sup.a                                                                        Fire.sup.b                                                                         Evaporation.sup.c                         Sample #                                                                            R.sub.1                                                                         R.sub.2                                                                             2 3   4  5  Point, °F.                                                                  Point, °F.                                                                  Loss, %                                   __________________________________________________________________________    1     H n-decyl                                                                             --                                                                              100%                                                                              -- -- 500  565  0.5                                       2     H n-decyl                                                                             --                                                                               45%                                                                              50%                                                                               5%                                                                              520  580  --                                        3     H n-decyl                                                                             --                                                                              --  67%                                                                              33%                                                                              550  620  --                                        4     H n-dodecyl                                                                           --                                                                              40  60%                                                                              -- 560  625  0.1                                       __________________________________________________________________________     .sup.a ASTM D92                                                               .sup.b ASTM D92                                                               .sup.c ASTM D972, 400° F., 6.5 hr., 2L/min N.sub.2                

EXAMPLE 11

To evaluate the hydrocarbon substituted cyclopentadienes for lubricatingproperties, tests were carried out to measure physical properties whichare relevant to use as a synthetic lubricant. Set forth in the followingTable 12 are viscosity and pour point properties of the identical alkylsubstituted cyclopentadienes. In the cyclopentadienes tested, R₁ ishydrogen, x is 2 to 6 and R₂ is as indicated.

                  TABLE 12                                                        ______________________________________                                        Viscometric Properties of Alkylcyclopentadienes                                                  Vis      Vis    Vis-  Pour.sup.c                                              (100° C.),                                                                      (40° C.),                                                                     cosity.sup.b                                                                        Point,                               Sample                                                                              R.sub.2 ═                                                                              cSt.sup.a                                                                              cSt.sup.a                                                                            Index °F.                           ______________________________________                                        1     n-Butyl      2.65     12.69  -3    <-60                                 2     n-Decyl      5.00     22.35  157      0                                 3     n-octyl/n-decyl                                                                            6.06     31.04  146     -5                                 4     2-octyl-1-dodecyl                                                                          12.78    93.38  133    -50                                 ______________________________________                                         .sup.a ASTM D445                                                              .sup.b ASTM D2270                                                             .sup.c ASTM D97                                                          

EXAMPLE 12 Preparation of Alkylcyclopentenes

The tri- and tetrasubstituted alkyl cyclopentadienes (a mixture ofn-octyl and n-decyl alkyl groups) were mildly hydrogenated over PD/C atambient temeprature. The alkylcyclopentadienes (350 g), 10% PD/Ccatalyst (3.0 g) and light hydrocarbon solvent (500 mL) were placed in a4-liter autoclave. After purging with hydrogen, the system waspressurized to 600 psig hydrogen. The system was stirred for 8 hours atroom temperature after which time the pressure dropped to 510 psig. Thesolution was filtered through a bed of Celite to remove the catalyst andthe solvent was removed in vacuo to afford 347 g of a yellowish oil.

Spectroscopic Characterization of Alkylcyclopentenes

Alkyl cyclopentenes produced by mild hydrogenation can be distinguishedspectroscopically from the alkylcyclipentanes and alkylcyclopentadienesin the following ways:

1. Ultraviolet Spectra--Alkylcyclopentadienes are characterized by anintense absorption at about 260 nm. This band disappears uponhydrogenation to alkylcyclopentanes, and another band, near 220 nm,appears. Upon further hydrogenation of the product alkylcyclopentenes,the 220 nm band disappears as the alkylcyclopentenes are converted intothe UV transparent alkylcyclopentanes.

2. ¹ H Nuclear Magnetic Response Spectra--Alkylcyclopentadienes showsresonances for the doubly allylic ring CH₂ 's and CHR's at 2.7 to 2.8ppm downfield of the tetramethylsilane. Upon hydrogenation, theseresonances disappear and additional resonances in the 1.6 to 2.0 ppmregion characteristic of singly allylic CH₂ 's and CHR's develop. Uponfurther hydrogentation of the alkylcyclopentenes, the intensity ofresonances in the 1.6 to 2.0 ppm region of the spectrum decrease as thealkylcyclopentenes are converted into alkylcyclopentanes.

3. ¹³ C Nuclear Magnetic Response Spectra--In the region of the spectrum110 to 160 ppm downfield from tetramethylsilane, a multitude ofresonances can be observed for alkylcyclopentadienes. Uponhydrogenation, these resonances disappear and new resonances in the 130to 145 ppm region of the spectrum characteristic of thealkylcyclopentenes appear. Upon further hydrogenation of thealkylcyclopentenes, the resonances in the 130 to 145 region of thespectrum disappear and the spectrum becomes transparent from 55 to 200ppm, as one would predict for a full saturated material. FIGS. 1 to 3are the ¹³ C nmr spectra of alkylcyclopentadiene, alkylcyclopentene, andalkylcyclopentane respectively.

                  TABLE 13                                                        ______________________________________                                        Physical Properties of Some Alkylcyclopentadienes.sup.a,                      Alkylcyclopentenes and Alkylcyclopentanes derived from them.                                                   Pour                                                     VISCOSITIES Viscosity                                                                              Point,                                                   100C, cSt                                                                            40C, cSt Index    deg F.                                   ______________________________________                                        Alkylcyclopentadiene 1                                                                      5.02     23.46    147      60                                   Alkylcyclopentene 1                                                                         5.10     24.29    144    <-65                                   Alkylcyclopentane 1                                                                         5.27     25.66    143    <-65                                   Alkylcyclopentadiene 2                                                                      6.06     31.04    146      -5                                   Alkylcyclopentene 2                                                                         6.09     31.39    145     -50                                   Alkylcyclopentane 2                                                                         6.33     34.17    138    <-65                                   Alkylcyclopentadiene 3                                                                      4.99     35.30     41     -71                                   Alkylcyclopentene 3                                                                         4.93     34.69     39     -71                                   Alkylcyclopentane 3                                                                         4.96     35.14     39     -71                                   ______________________________________                                         .sup.a Alkylcyclopentadienes 1 and 2 are different products prepared by       the alkylation of cyclopentadiene with a mixture of noctanol and ndecanol     Alkylcyclopentadiene 3 was prepared by alkylation of cyclopentadiene with     2ethylhexanol.                                                           

The synthetic lubricating compositions of the present invention are usedas lubricants by blending with one or more additives conventionally usedwith lubricating oil obtained from natural sources or other types ofsynthetic lubricating oil. Thus, there may be included within thesynthetic lubricating oil of this invention from 0.01 up to about 40% byweight of conventional pour point depressants, viscosity indeximprovers, dispersants, load carrying agents, rust inhibitors, andanti-oxidants, as well as mixtures of such conventional additives. Itwill be understood that the synthetic lubricants of this invention willbe mixed with the number of additives and amounts to provide goodperformance, particularly when used in internal combustion engines.Particular additives which may be used include polymethacrylates whichare well known as pour point depressants and viscosity index improverssuch as hydrogenated diolefin-lower alkyl acrylate or methacrylatecopolymers. Other additives which may be blended with the lubricants ofthe invention include zinc dialkyl dithiophosphates, phenates,sulfonates, non-ionic dispersants, such as alkyl succinimides or Mannichbases of phenols, polyacrylate and methacrylate pour point depressants,and olefin copolymer or polyacrylate viscosity index improvers, or anyother effective motor oil additives.

The synthetic lubricating oil of this invention may be blended in amountranging from about 5% to 95% with a lubricant obtained from naturalsources such as a refined paraffin-type base oil, a refinednapthenictype base oil, asphaltic or mixed base crude and/or mixturesthereof. The viscosity of such oils may vary over a wide range such asfrom 70 SUS at 100° F. to 300 SUS at 210° F. and the boiling point ofthese oils may vary over a wide range as from 300°-750° F.

The synthetic lubricants of the present invention may also be blendedwith other synthetic lubricating oils such as those obtained bypolymerization of lower molecular weight alkenes, as well as esters,phosphates and silicon-based lubricants. The blends with other syntheticlubricants will range from 5 to 95%. Mixtures of one or more othernatural or synthetic lubricants may also be employed in the sameproportions.

The following examples illustrate such mixtures and blends.

EXAMPLE 13

Engine oils are prepared by mixing:

1. an alkylcyclopentane,

2. a commercially available ester, such as Emery 2971,

3. a commercial detergent-inhibitor additive, such as Lubrizol 7608,

4. a commercial viscosity index improver, such as Texaco TLA 656,

5. a commercial phenolic antioxidant, such as Ethyl 728.

A typical formulation is shown in Table 14.

                  TABLE 14                                                        ______________________________________                                        Engine Oil made with Alkylcyclopentane Base Oil                                                   % by weight                                               ______________________________________                                        Formulation                                                                   Alkylcyclopentane*    57.3                                                    Emery 2971            24.0                                                    Lubrizol 7608         11.5                                                    TLA 656                7.0                                                    Ethyl 728              0.2                                                    Properties                                                                    Viscosity, 100° C.                                                                           10.99 cSt                                               Viscosity Index       171                                                     Cold Cranking Simulator                                                                             2250 cP                                                 Viscosity, -25° C.                                                     SAE Grade             5W-30                                                   ______________________________________                                         *Prepared from cyclopentadiene and Ethyl Corporation's EPAL 810, a            commercially available mixture of noctanol and ndecanol, by the method        described in this disclosure. Properties of this particular base oil are      Viscosity (100° C.) = 5.23 cSt; Viscosity Index = 134.            

EXAMPLE 14

A proprietary engine test was carried out on three oils:

1. The 5W-30 motor oil based on alkylcyclopentane base oil described inExample 13,

2. a commercially available, fully synthetic, PAO/ester based, 5W-30motor oil,

3. a commercially available, mineral oil based, 5W-30 motor oil.

The results are summarized in Table 15.

                  TABLE 15                                                        ______________________________________                                        Results of Engine Tests on 5W-30 Motor Oils                                              Oil of  Commercial Commercial                                                 Table 14                                                                              Synthetic  Mineral Oil                                     ______________________________________                                        % Viscosity  6         27         590                                         Increase at 70 hrs.                                                           Rocker Arm Sludge*                                                                         9.50      9.65       9.54                                        Piston Skirt Varnish*                                                                      8.3       8.6        8.0                                         Oil Ring Land*                                                                             6.88      6.84       5.14                                        Face Deposits                                                                 Oil Consumption, lbs.                                                                      1.12      1.26       4.62                                        ______________________________________                                         *Rating, maximum merit score of 10.                                      

EXAMPLE 15

Engine oils were prepared by mixing:

1. an alkylcyclopentane,

2. commercial neutral mineral oils,

3. a commercial detergent-inhibitor additive, such as Lubrizol 7608,

4. a commercial viscosity index improver, such as Texaco TLA 656,

5. a commercial pour point depressant, such as Acryloid 154-70.

A typical formulation is shown in Table 16.

                  TABLE 16                                                        ______________________________________                                        Engine Oil Made with Alkylcyclopentane and Mineral Oil                                            % by weight                                               ______________________________________                                        Formulation                                                                   Alkylcyclopentane*    25.8                                                    Mineral Oil (100 Neutral)                                                                           42.7                                                    Mineral Oil (300 Neutral)                                                                           11.8                                                    Lubrizol 7608         11.5                                                    TLA 656                8.0                                                    Acryloid 154-70        0.2                                                    Properties                                                                    Viscosity, 100° C.                                                                           11.55 cSt                                               Viscosity Index       157                                                     Cold Cranking Simulator                                                                             3400 cP                                                 Viscosity, -25° C.                                                     Pour Point            -30° F.                                          SAE Grade             5W-30                                                   ______________________________________                                         *Same base oil as that in Example 13 (see Table 14).                     

The application has been described with reference to certain preferredembodiments. However, as obvious variations thereon will become apparentto those skilled in the art, the invention is not to be considered aslimited thereto.

We claim:
 1. A synthetic lubricating composition comprising:(A) Asynthetic lubricant comprising:(1) a hydrocarbyl substitutedcyclopentane; (2) a hydrocarbyl substituted cyclopentadiene; (3) ahydrocarbyl substituted cyclopentene; or (4) mixtures in any proportionsof (1), (2), and (3); in admixture with (B) a natural lubricant or asynthetic lubricant other than a member of (A); and (C) an effectiveamount of at least one lubricating oil additive selected from the groupconsisting of pour point depressants, viscosity index improvers,dispersants, load carrying agents, rust inhibitors, anti-oxidants, andmixtures thereof.
 2. A composition according to claim 1 wherein thecomposition contains 5 to 95 wt. % of (A) and 95 to 5 wt. % of (B).
 3. Acomposition according to claim 1 wherein the natural lubricant is amineral oil.
 4. A composition according to claim 1 wherein the syntheticlubricant is a poly-alpha-olefin, ester, polyol ester, or mixturethereof.
 5. A lubricating composition according to claim 1 wherein thesynthetic lubricant of (A) is cyclopentane substituted by at least twohydrocarbyl groups having 4 to 36 carbon atoms.
 6. A syntheticlubricating composition according to claim 5 whererin the syntheticlubricant component (A) comprises at least one cyclopentane of thefollowing formula: ##STR25## wherein each R₁ is individually andindependently selected from an alkyl groups of 1 to 4 carbons, each R₂is individually and independently selected from straight or branchchained hydrocarbyl groups containing from 4 to 36 carbon atoms, z is 0,1, 2 or 3, and x is an integer ranging from 2 to 6, and x+z cannot begreater than
 6. 7. A lubricating composition according to claim 1wherein the synthetic lubricant of (A) is cyclopentadiene substituted byat least two hydrocarbyl groups having 4 to 36 carbon atoms.
 8. Asynthetic lubricating composition according to claim 7 wherein thesynthetic lubricant (A) comprises at least one cyclopentadiene of thefollowing formula: ##STR26## wherein each R₁ is individually andindependently selected from alkyl groups of 1 to 4 carbon atoms, each R₂is individually and independently selected from straight or branchchained hydrocarbyl groups having 4 to 36 carbon atoms, z is 0, 1, 2 or3, x is an integer ranging from 2 to 6, and x+z cannot be greater than6.
 9. A synthetic lubricating composition according to claim 8 whereinthe synthetic lubricant of (A) is at least one cyclopentene of thefollowing formula: ##STR27## wherein each R₁ is individually andindependently selected from alkyl groups of 1 to 4 carbon atoms, each R₂is individually and independently selected from hydrocarbyl groupscontaining 4 to 36 carbon atoms, z is 0, 1, 2 or 3, and x is an integerof 2 to 6, and x+z cannot be greater than
 6. 10. A synthetic lubricatingcomposition according to claim 1 wherein the natural lubricant of (B) isa natural lubricant selected from the group consisting of paraffin-typebase oils, asphaltic or mixed base crude oils, and mixtures thereof. 11.A synthetic lubricating composition according to claim 1 wherein thesynthetic lubricant of (B) is selected from the group consisting ofpolymerized lower molecular weight alkenes, polymerized esters,phosphates, silicon based lubricants, and mixtures thereof.
 12. Asynthetic lubricating composition according to claim 1 wherein thelubricating oil additive is contained in the composition in an amountranging from about 0.01 up to about 40% by weight of the totalcomposition.
 13. A synthetic lubricating composition according to claim12 wherein the additive is selected from the group consisting of pourpoint depressants, viscosity index improvers, dispersants, load carryingagents, anti-oxidants and mixtures thereof.
 14. A synthetic lubricatingcomposition according to claim 12 wherein the additive is selected fromthe group consisting of zinc dialkyl dithiophosphates, phenates,sulfonates, non-ionic dispersants, polyacrylate pour point dispersants,methacrylate pour point dispersants, olefin copolymer viscosity indeximprovers, polyacrylate viscosity index improvers, and mixtures thereof.15. A synthetic lubricating composition according to claim 9 wherein thelubricating oil additive is contained in the composition in an amountranging from about 0.01 up to about 40% by weight of the totalcomposition.
 16. A synthetic lubricating composition according to claim15 wherein the additive is selected from the group consisting of pourpoint depressants, viscosity index improvers, and mixtures thereof. 17.A synthetic lubricating composition according to claim 1 wherein theadditive is selected from the group consisting of zinc dialkyldithiophosphates, phenates, sulfonates, non-ionic dispersants, pointdispersants, olefin copolymer viscosity index improvers, polyacrylateviscosity index improvers, and mixtures thereof.